CN104271453B - Blow-molded container with compressed part - Google Patents
Blow-molded container with compressed part Download PDFInfo
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- CN104271453B CN104271453B CN201380024813.8A CN201380024813A CN104271453B CN 104271453 B CN104271453 B CN 104271453B CN 201380024813 A CN201380024813 A CN 201380024813A CN 104271453 B CN104271453 B CN 104271453B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
Abstract
A kind of blow-molded container, it is characterised in that it is the blow-molded container with compressed part, has in innermost layer and contains ethylene-vinyl alcohol copolymer（A）And supple resin（B）Resin composition layer；Supple resin（B）For styrene series thermoplastic elastomer or alpha olefin copolymer, ethylene-vinyl alcohol copolymer（A）With supple resin（B）Mass ratio [（A）/（B）] in the range of 75/25 ~ 90/10, with ethylene-vinyl alcohol copolymer（A）For matrix phase, supple resin（B）It it is less than 0.3 μm for the particle wall spacing of the island structure of dispersed phase, and foregoing dispersed phase.
Description
Technical field
The present invention relates to innermost layer have containing ethylene-vinyl alcohol copolymer it is resin composition layer, with compressed part
（pinch-off part）Blow-molded container.
Background technology
Ethylene-vinyl alcohol copolymer（Hereinafter, also referred to as EVOH sometimes）Due to showing excellent resistance to gases such as oxygen
Every property and melt-moldability is also excellent, therefore it is formed as film, bottle etc. and is widely used as various packaging materials etc..EVOH is due to tool
There is high crystalline and impact strength is low, in order to be made up to it, be laminated mostly with the excellent thermoplastic resin such as mechanical property
To use.Especially, in the fields such as blow-molded container, the widely used resin composition layer having containing EVOH and poly- second
The sandwich construction of the layer of the polyolefin-based resins such as alkene, polypropylene.
For example, in Japanese Patent Laid-Open No. Sho 57-32952 publications, as with chemical proofing and low gas permeation
The container of property, is described using evoh layer as intermediate layer, ectonexine passes through multi-layer co-extruded blow molding method as polyolefin layer
The laminated vessel being molded.But, the laminated vessel is poor due to the organic solvent resistance of the polyolefin layer of innermost layer, therefore
During using organic solvent etc. as content, the container impact resistance reduction after deterioration, long-term keeping is produced sometimes.
By the way that innermost layer is made into evoh layer, the organic solvent resistance of container can be improved.But, innermost layer is used
EVOH container is only capable of being laminated polyolefin layer in the one side of evoh layer, therefore impact resistance becomes insufficient, can not wanted sometimes
Used in the purposes for seeking high-impact.Thus, one kind is proposed in Japanese Patent Laid-Open 2010-95315 publications most interior
Layer has the agriculture pharmaceutical containers of resin composition layer, and the resin composition layer contains EVOH and with polyalkylene ether unit
Polymer.It is said that the low-temperature impact resistance of the agricultural chemicals container is excellent.
Prior art literature
Patent document
Patent document 1：Japanese Patent Laid-Open No. Sho 57-32952 publications
Patent document 2：Japanese Patent Laid-Open 2010-95315 publications.
The content of the invention
Problems to be solved by the invention
For the blow-molded container with compressed part, in order that under during blow-molded container tolerance actual use
The impact such as fall, not only need to utilize notched cantilever-type impact strength（izod impact strength）And the appearance evaluated
The side bottom surface of device, the impact strength in corner, in addition it is also necessary to the impact strength of pressed parts.Especially, for using evoh layer as
For intermediate layer and ectonexine is the blow-molded containers of polyolefin layer, compressed part be to be formed innermost layer polyolefin it is fused with one another
Formed by, on the other hand, for the blow-molded container that innermost layer has used the resin combination containing EVOH, compressed part
Position is formed by EVOH fused with one another.The present inventor etc. recognizes when being studied：Such as Japanese Patent Laid-Open 2010-95315
Described in number publication notched beam type is utilized like that into EVOH during polymer of the compounding with polyalkylene ether unit
The impact resistance that impact strength is evaluated is improved, but the impact strength of pressed parts reduces, is used as blow molding sometimes
The impact resistance of container is insufficient.
The present invention be in view of such situation and carry out, its object is to there is provided a kind of blow-molded container, its be
Innermost layer has used the blow-molded container of the resin combination containing EVOH, side bottom surface, the impact strength and compressed part in corner
The impact strength divided is excellent, and the impact such as whereabouts during to actual use has high patience.
The solution used to solve the problem
Invention for solving above-mentioned problem and carrying out is：
Blow-molded container, it is characterised in that it is the blow-molded container with compressed part, it has in innermost layer contains
Ethylene-vinyl alcohol copolymer（A）And supple resin（B）Resin composition layer；Supple resin（B）For polystyrene thermoplastic elastomehc
Property body or alpha olefin copolymer, ethylene-vinyl alcohol copolymer（A）With supple resin（B）Mass ratio [（A）/（B）] 75/25 ~
In the range of 90/10, with ethylene-vinyl alcohol copolymer（A）For matrix phase, supple resin（B）For the island structure of dispersed phase,
And the particle wall spacing of foregoing dispersed phase is less than 0.3 μm.
The resin composition layer passes through with EVOH（A）For matrix phase and supple resin（B）For the island structure of dispersed phase,
And the particle wall spacing of above-mentioned dispersed phase is less than 0.3 μm of structure, energy when applying impact can be had by supple resin
Effect ground disperses, and side bottom surface, the corner of the blow-molded container show excellent impact strength.In addition, by using specific
Resin is used as supple resin（B）And then by EVOH（A）With supple resin（B）It is compounded with specific ratio, so as to realize
The taking into account of the impact strength of the side bottom surface of the blow-molded container, the impact strength in corner and pressing section.
The melt flow rate (MFR) of the aforementioned resin measured under 210 DEG C, 2160g loads（MFR）Preferably ethene-
Ethenol copolymer（A）Melt flow rate (MFR)（MFR）Less than 2/3.
The supple resin measured according to ISO 7619（B）A type Shore hardness（デ ュ ロ メ ー タ ー タ イ プ A are hard
Degree）Preferably less than 90.It is used as supple resin（B）, by meeting above-mentioned condition, can more effectively disperse impact energy, energy
Enough side bottom surface, impact strengths in corner for further improving the blow-molded container.
Supple resin（B）Preferably acid is modified supple resin（b1）With unmodified supple resin（b2）Mixture.Prepare
During above-mentioned resin combination, pass through EVOH（A）With supple resin（B）React, meet above-mentioned condition, can further improve
The side bottom surface of the blow-molded container, the impact strength in corner.
The blow-molded container of the present invention is preferably used as flask for medicinal preparations.The oxygen-barrier property of the flask for medicinal preparations, drug resistance be excellent,
The impact of whereabouts during to actual use etc. has high patience.
As above-mentioned medicament, agricultural chemicals is preferably used, blow-molded container of the invention is preferably used as pesticide bottle.The pesticide bottle
Oxygen-barrier property, organic solvent resistance it is excellent, whereabouts during to actual use etc. impact have high patience.
The effect of invention
According to the present invention, it is possible to provide following blow-molded container, it is to have used the resin group containing EVOH in innermost layer
The blow-molded container of compound, not only side bottom surface, corner impact strength it is excellent, the impact strength of pressing section is also excellent,
The impact of whereabouts during to actual use etc. has high patience.The blow-molded container can be suitably used as flask for medicinal preparations, outstanding
It is pesticide bottle.
Embodiment
Hereinafter, the embodiment for the blow-molded container of the present invention is illustrated.It should be noted that following explanation
In, specific material is exemplified sometimes as the material for showing specific function, but workable material is not limited in the present invention
Due to them.In addition, illustrated material can be used alone, can also combine makes in the case of no especially record
With two or more.
[resin combination]
The resin combination used in the innermost layer of the blow-molded container of the present invention contains EVOH with specific mass ratio
（A）, supple resin（B）.The resin combination can further contain other compositions.
[EVOH（A）]
EVOH（A）It is the copolymer mainly with ethylene unit and vinyl alcohol units.EVOH（A）Base catalysis for example can be used
The copolymer being made up of ethene and vinyl esters is carried out saponification and obtained by agent etc..As vinyl esters, it can be enumerated as representing
Go out vinyl acetate, other fatty acid ethylene base esters can also be used（Propionate, new vinyl acetate acid etc.）.
In addition, EVOH（A）In, for example can the vinyl silanes containing 0.0002 ~ 0.2 mole of % as copolymer composition
Compound.Herein, as vinyl silanes based compound, such as vinyltrimethoxy silane, the ethoxy of vinyl three can be included
Base silane, vinyl three（'beta '-methoxy-ethyoxyl）Silane, γ-（Methyl）Acryloxypropyl methoxy silane.These it
In, it can compatibly use vinyltrimethoxy silane, VTES.And then, EVOH（A）Do not damaging this hair
Can have in the range of improving eyesight with copolymerization other comonomers, such as propylene, butylene or（Methyl）Acrylic acid,（Methyl）
Methyl acrylate or（Methyl）The vinylpyridine such as the unsaturated carboxylic acids such as ethyl acrylate or its ester and NVP
Pyrrolidone.
EVOH（A）Ethylene unit containing ratio be preferably 20 moles of more than % and 60 mole of below %, more preferably 25 moles %
Above and 55 moles of below %, more preferably 27 moles of more than % and 50 mole of below %.Acetate unit content rate is rubbed less than 20
During your %, the melt-moldability of the resin combination can be reduced.On the contrary, when ethylene unit containing ratio is more than 60 moles of %, gained
The barrier properties for gases of blow-molded container can be reduced.
In addition, EVOH（A）Saponification degree be not particularly limited, preferably 90 moles more than %, more preferably 95 moles of % with
Upper, more preferably 99 moles of more than %.From the viewpoint of the barrier properties for gases for maintaining gained blow-molded container, make
EVOH（A）Saponification degree be in above range be preferred.
On EVOH（A）Melt viscosity, 210 DEG C, 2160g load under melt flow rate (MFR)（MFR）Preferably 1.0
~ 100g/10 minutes, more preferably 2.0 ~ 60g/10 minutes, more preferably 3.0 ~ 30g/10 minutes.By using this molten
The EVOH of melt-viscosity（A）, can further improve melt-moldability of the resin combination etc..
EVOH（A）It may be used singly or in combination of two or more.
[modified EVOH（A’）]
It is used as EVOH（A）, can also use EVOH epoxides（E）Ethene improved obtained from being modified-
Ethenol copolymer（A’）（Hereinafter, " modified EVOH is abbreviated as sometimes（A’）”）.Modified EVOH（A’）Crystallinity is low and softness,
Therefore the side bottom surface of the blow-molded container, corner impact strength it is excellent.
Modified EVOH（A’）It is by EVOH epoxides（E）Obtained from being modified, can include for example makes ring
Oxygen compound（E）With the modification EVOH of EVOH hydroxyl reaction（A’）.
Such modified EVOH（A’）Can be by making EVOH and epoxide（E）React and obtain in extruder.
It should be noted that when now excessively containing alkali metal salt and/or alkali salt in raw material EVOH, gained is modified EVOH
（A’）It is possible to coloring or causes to be modified EVOH because viscosity is reduced（A’）Melt-moldability reduction.In addition, as described later
Like that, carried out using catalyst during above-mentioned reaction, alkali metal salt and/or alkali salt can lose above-mentioned catalyst sometimes
It is living.Therefore, alkali metal salt and/or the content of alkali salt in raw material EVOH is preferably few as much as possible.
It is used as above-mentioned epoxide（E）, there is the epoxide of 1 epoxy radicals preferably in molecule.Epoxy compound
Thing（E）Molecular weight be preferably less than 500.Intramolecular have more than the binary of more than 2 epoxy radicals epoxide with
When EVOH reacts, cross-linking reaction is caused sometimes.
On epoxide（E）, it is preferred that the part being excessively added when will easily can be modified is modified from gained
EVOH（A’）It is middle to remove.As one of such minimizing technology, epoxide of sening as an envoy to can be enumerated（E）From the passage of extruder
The method of volatilization, therefore epoxide（E）Boiling point be preferably less than 250 DEG C, more preferably less than 200 DEG C.In addition, epoxy
Compound（E）Carbon number be preferably 2 ~ 10.It is used as such epoxide（E）Concrete example, epoxy second can be included
Alkane, 1,2 epoxy prapane, 1,2- epoxy butanes, glycidol, 1,2- epoxy -3- butylene, 1,2- epoxy -4- amylenes, 1,2- rings
Oxygen -5- hexenes, 1,2- epoxy -4- vinyl cyclohexanes, allyl glycidyl ether, methacrylic glycidol ether, second two
Alcohol allyl glycidyl ether etc., preferably 1,2- expoxy propane, 1,2- epoxy butanes, allyl glycidyl ether.And then, make
For other methods of above-mentioned minimizing technology, the method for carrying out washing removal from the passage of extruder, now, epoxy can be included
Compound（E）It is preferably soluble in water.
EVOH（A）With epoxide（E）Reaction condition be not particularly limited, preferably with International Publication No. 02/
Method described in No. 092643 is similarly carried out in extruder.Now, preferably add catalyst, in this case, it is preferred that
The catalyst deactivators such as carboxylate are added after reaction.For the EVOH resins addition epoxidation in molten condition in extruder
Compound（E）When, epoxide can be prevented（E）Be vaporized, and be easily controlled reacting dose, so it is preferred that.
Modified EVOH（A’）In epoxide（E）Modified monomeric unit of the amount relative to EVOH total mole number it is excellent
Elect 0.1 ~ 10 mole of %, more preferably 0.3 ~ 5 mole %, more preferably 0.5 ~ 3 mole of % as.Less than 0.1 mole % of modified amount
When, it is possible to cannot be by the modified effect brought.On the other hand, when modified amount is more than 10 moles of %, heat endurance is possible to drop
It is low.
[supple resin（B）]
It is used as supple resin（B）, styrene series thermoplastic elastomer or alpha olefin copolymer can be used.By the way that these are set
Fat is used as supple resin（B）, side bottom surface, the impact strength in corner and the pressing section of gained blow-molded container can be achieved
Impact strength is taken into account.Among these, from low temperature under flexibility is excellent, the side bottom in a low temperature of the blow-molded container
From the viewpoint of face, the impact strength in corner are improved, alpha olefin copolymer is preferably used.
（Styrene series thermoplastic elastomer）
As styrene series thermoplastic elastomer, it is not particularly limited, known elastomer can be used.Polystyrene heat
Thermoplastic elastic generally has the styrene monomer polymer blocks as hard segment（Hb）With the conjugated diene as soft chain segment
Compound polymer block or its hydrogenated block（Sb）.Can be Hb-Sb as the structure of the styrene series thermoplastic elastomer
Four block knots shown in three block structure, Hb-Sb-Hb-Sb shown in shown diblock structure, Hb-Sb-Hb or Sb-Hb-Sb
Structure or the poly block structure that straight-chain is bonded to by the Hb and Sb that amount to more than 5.
It is used as above-mentioned styrene monomer polymer blocks（Hb）The middle styrenic monomers used, are not particularly limited, can
Include Styrene and its derivatives etc..Specifically, such as styrene, α-methylstyrene, 2- methylbenzene second can be included
Alkene, 4- methyl styrenes, 4- propylstyrenes, 4- t-butyl styrenes, 4- cyclohexylstyrenes, 4- dodecylstyrenes,
2- ethyl -4- benzylstyrenes, 4-（Phenyl butyl）Styrene, 2,4,6- trimethyl styrenes, single fluorobenzene ethene, difluorobenzene second
The phenylethylenes such as alkene, monochlorostyrene, dichlorostyrene, methoxy styrene, t-butoxystyrene；1- vinyl naphthalenes, 2-
Vinyl naphthalenes such as vinyl naphthalene etc. contain vinyl aromatic compounds；Compounds containing vinylidene aromatic such as indenes, acenaphthene etc..This
Among a little, preferably styrene.Styrenic monomers can be only one kind, or two or more.
In addition, above-mentioned conjugated diene compound polymer blocks（Sb）The middle conjugated diene compound used is also without special
Limit.As such conjugated diene compound, butadiene, isoprene, 2,3- dimethyl butadienes, penta 2 can be included
Alkene, hexadiene etc..Among these, preferably butadiene.Conjugated diene compound can be only one kind, or two kinds with
On.And then, can also the other comonomers of copolymerization, such as ethene, propylene, butylene, styrene.In addition, conjugated diene compound
Polymer blocks（b2）It can also be the hydrogenation thing being hydrogenated with partially or completely.
The styrene monomer polymer blocks unit of styrene series thermoplastic elastomer（Hb）Containing ratio be usually 5 matter
More than % and below 80 mass % are measured, from the viewpoint of the impact strength in the side bottom surface of the blow-molded container, corner is improved,
Preferably more than 10 mass % and below 50 mass %, more preferably more than 20 mass % and below 40 mass %.
The conjugated diene compound polymer blocks and/or its hydrogenated block of styrene series thermoplastic elastomer（Sb）Contain
It is usually more than 20 mass % and below 95 mass % to have rate, the impact strength from the side bottom surface of the blow-molded container, corner
From the viewpoint of raising, preferably more than 50 mass % and below 90 mass %, more preferably more than 60 mass % and 80 mass % with
Under.
As the concrete example of styrene series thermoplastic elastomer, styrene-isoprene diblock copolymer can be included
（SI）, styrene-butadiene diblock copolymer（SB）, SIS（SIS）, benzene
Ethylene-butylene/isoprene styrene triblock copolymer（SB/IS）And s-B-S three block
Copolymer（SBS）And its hydrogenation thing.Especially, from the viewpoint of weatherability etc. is excellent, preferably styrene-isoprene two
The hydrogenation thing of block copolymer（SEP）, styrene-butadiene diblock copolymer hydrogenation thing（SEB）, styrene-isoamyl two
The hydrogenation thing of alkene-styrene triblock copolymer（SEPS）, styrene-butadiene/isoprene styrene triblock copolymer
Hydrogenation thing（SEEPS）And the hydrogenation thing of SBS（SEBS）, it is blow molded into from this
From the viewpoint of the side bottom surface of type container, the impact strength in corner are improved, particularly preferably s-B-S
The hydrogenation thing of triblock copolymer（SEBS）.
（Alpha olefin copolymer）
As alpha olefin copolymer, it is not particularly limited, ethylene-propylene copolymer can be included（EP）, Ethylene/Butylene it is common
Polymers（EB）, propene-1-butene copolymer（PB）, butene-ethylene copolymer（BE）Deng.Among these, from flexibility is excellent, this blows
Mould the side bottom surface of container molding, from the viewpoint of the impact strength in corner improves, preferably ethylene-propylene copolymer（EP）、
Ethylene-butene copolymer（EB）, it is especially excellent from the viewpoint of the impact strength of the pressing section of the blow-molded container is improved
Elect ethylene-butene copolymer as（EB）.
From can further improve the side bottom surface of melt-moldability and the blow-molded container, the impact strength in corner
Viewpoint is set out, the supple resin used in the present invention（B）Preferably acid is modified supple resin（b1）With unmodified supple resin
（b2）Mixture.
The modified supple resin of acid used in the present invention（b1）Be by above-mentioned styrene series thermoplastic elastomer or above-mentioned α-
Olefin copolymer carries out what acid was modified.
Herein, acid modification is carried out as follows：By the way that alpha olefin copolymer or styrene series thermoplastic elastomer will be constituted
The part of monomer be substituted for α, beta-unsaturated carboxylic acid or its anhydride monomers and carry out copolymerization, or pass through free radical addition etc.
Graft reaction etc. imports α, beta-unsaturated carboxylic acid or its acid anhydrides to a part for side chain, so as to carry out.
The α used as above-mentioned acid in modified, beta-unsaturated carboxylic acid or its acid anhydrides, can include maleic acid, acrylic acid, clothing
Health acid, crotonic acid, maleic anhydride, itaconic anhydride etc..Wherein, it is adapted to use maleic anhydride.
The modified supple resin of acid（b1）Acid number be preferably below 50mgKOH/g, more preferably more than 1mgKOH/g and
Below 30mgKOH/g, more preferably more than 2mgKOH/g and below 20mgKOH/g.Acid number be higher than the scope when, exist as
Lower tendency：With EVOH（A）In hydroxyl reaction site increase, high polymerization degree compound is generated during melting mixing, is blow molded into
Melt-moldability, heat endurance during type etc. can be reduced.On the other hand, when acid number is less than the scope, with EVOH（A）Compatibility
It is likely to decrease, sufficient impact resistance can not be obtained.
On supple resin（B）Melt viscosity, 210 DEG C, the lower MFR of 2160g loads be preferably that 1.0 ~ 100g/10 divides
Clock, more preferably 2.0 ~ 60g/10 minutes.By using the supple resin of such melt viscosity（B）, can further improve
The side bottom surface of melt-moldability, the blow-molded container during blow molding, the impact strength in corner.
It is used as EVOH（A）With supple resin（B）210 DEG C, 2160g load under MFR difference, preferably 30g/10 minutes
Below, it is more preferably less than 10g/10 minutes.Like this, EVOH（A）Melt viscosity and supple resin（B）Melt viscosity get over
Close, then melting mixing becomes easier, easier in supple resin（B）In EVOH（A）The scattered state of middle differential.If
Contain EVOH using such（A）And supple resin（B）Resin combination, then be readily available the impact in side bottom surface, corner
The blow-molded container of excellent strength.
On the supple resin used in the present invention（B）The A type Shore hardness measured according to ISO 7619, from resin
The dispersion effect of impact energy in composition improves, can further improve side bottom surface, the corner of the blow-molded container
Impact strength from the viewpoint of, preferably less than 90, more preferably less than 86, more preferably less than 70, particularly preferably
For less than 67.
[mix ratio]
In resin combination used in the present invention, for the impact of the side bottom surface, corner of taking into account blow-molded container
Intensity and the impact strength of pressing section are, it is necessary to make EVOH（A）With supple resin（B）Mass ratio [（A）/（B）] for 75/25 ~
90/10.EVOH（A）Content be less than the scope when, the impact strength of pressing section can be reduced.Mass ratio [（A）/（B）] preferably
For more than 80/20.On the other hand, EVOH（A）Content be more than the scope when, side bottom surface, the angle of gained blow-molded container
The impact strength in portion can be reduced.Mass ratio [（A）/（B）] it is preferably less than 85/15.
In above-mentioned resin combination, supple resin（B）It can be the modified supple resin of acid（b1）Monomer, is preferably that acid is modified
Supple resin（b1）With unmodified supple resin（b2）Mixture.During as mixture, the modified supple resin of acid（b1）With not
Modified supple resin（b2）Mass ratio [（b1）/（b2）] from improve blow-molded container side bottom surface, corner impact it is strong
It is preferably 1/99 ~ 99/1 from the viewpoint of degree.The modified supple resin of acid（b1）Content be more than the scope when, above-mentioned resin combination
The melt-moldability of thing reduces, easily produces flake in blow molding.In addition, the flake turns into starting point and causes blow molding
Container is easily damaged.Mass ratio [（b1）/（b2）] it is more preferably less than 67/33, more preferably less than 50/50.The opposing party
Face, the modified supple resin of acid（b1）Content be less than the scope when, EVOH（A）With supple resin（B）Compatibility become not fill
Point, it is difficult to acquisition has carried out microdispersed island structure, the impact strength meeting of the side bottom surface, corner of gained blow-molded container
Reduction.Mass ratio [（b1）/（b2）] it is more preferably more than 10/90, more preferably more than 25/75, particularly preferably 30/70
More than.
It is considered that：In the resin combination, it can be used as supple resin（B）The modified supple resin of acid（b1）Not only have
Have and EVOH（A）High-compatibility, can also play EVOH（A）With unmodified supple resin（b2）Compatilizer effect.With double
When screw extruder is to knead, prepare the resin combination, pass through the modified supple resin of acid（b1）In the acid and EVOH that include（A）
In hydroxyl react, EVOH is generated in an extruder（A）With the modified supple resin of acid（b1）Graft polymers.The grafting
Polymer has and EVOH（A）Compatibility, and then show EVOH（A）With unmodified supple resin（b2）Com-patibilising effect.
Thus, supple resin（B）In EVOH（A）Middle differential is dissipated, and the side bottom surface of the blow-molded container, the impact strength in corner are carried
It is high.
On the other hand, by generating graft polymers, the winding of strand can increase, thus with the EVOH as matrix
（A）MFR compare, exist the resin combination MFR reduction tendency.From com-patibilising effect become fully, EVOH（A）In it is soft
Barras（B）Dispersiveness become good from the viewpoint of, the MFR of the resin combination is preferably EVOH（A）MFR 2/3
Below.In addition, the MFR of resin combination reaches EVOH（A）MFR more than 1/10 and 3/5 the following is it is furthermore preferred that further
Preferably more than 1/5 and less than 1/2.When the MFR of resin combination is less than the scope, the melt-moldability drop of the resin combination
Easily flake is produced during low, blow molding.On the other hand, when the MFR of resin combination exceedes the scope, it is possible to be graft-polymerized
The generation of thing is insufficient, is difficult to obtain and has carried out microdispersed island structure, the side bottom surface of the blow-molded container, corner
Impact strength can be reduced.
Such mass ratio contains EVOH more than（A）And supple resin（B）The resin combination to maintain EVOH former
Originally the melt-moldability having.Specifically, 210 DEG C of the resin combination, the melt flow rate (MFR) under 2160g（MFR）It is excellent
Elect as 0.3 ~ 100g/10 minutes, more preferably 0.5 ~ 60g/10 minutes, more preferably 1.0 ~ 30g/10 minutes.By making
Above range is reached as the MFR of the resin combination, failure when melt molding is processed is few, result in outward appearance blowing well
Mould container molding.
[particle wall spacing]
The resin combination used in the present invention has EVOH（A）For matrix phase and supple resin（B）For the sea of dispersed phase
Island structure.By the way that with such island structure, side bottom surface, the impact strength in corner of gained blow-molded container can be achieved
With taking into account for the impact strength of pressing section.
Supple resin in the resin combination（B）Particle wall spacing in order to show the side of blow-molded container
Bottom surface, the impact strength in corner and need for less than 0.30 μm.Particle wall spacing is preferably less than 0.20 μm, is more preferably
Less than 0.15 μm.When particle wall spacing is more than 0.30 μm, impact resistance becomes insufficient.Particle wall spacing can for example lead to
Cross adjustment EVOH（A）With supple resin（B）Compounding ratio or supple resin（B）In the modified supple resin of acid（b1）With
Unmodified supple resin（b2）Compounding ratio control.
In the resin combination, EVOH（A）In supple resin（B）The particle wall spacing d of discrete particles can pass through
With following formula（I）By EVOH（A）With supple resin（B）Compounding ratio, EVOH（A）In supple resin（B）Dispersion particle diameter come
Calculate.
[mathematical expression 1]
Above-mentioned formula（I）In, r is supple resin（B）The radiuses of discrete particles, V be supple resin（B）Volume fraction.
The radius of above-mentioned discrete particles can be confirmed as follows：Gained resin composition layer is impregnated in into dimethylbenzene etc. to dissolve
Supple resin（B）Solvent, make supple resin（B）After dissolution, it is using the multiplying power by observations such as scanning electron microscopes
3000 times of image is confirmed.The radius of discrete particles can use ruler etc. on image direct measurement or by using scheme
Obtained as the diameter for the discrete particles that processing is calculated.
[other compositions]
The resin combination preferably comprises the chemical combination such as various acid, metal salt from the viewpoint of adjustment heat endurance, viscosity
Thing.Be alkali metal salt, carboxylic acid, phosphate cpd and boron compound etc. as the compound, can be included as concrete example with
Under composition.It should be noted that these compounds can be used in advance and EVOH sometimes（A）The compound of the state of mixing.
Alkali metal salt：Sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, odium stearate, potassium stearate, ethylenediamine tetra-acetic acid
Sodium salt etc.
Carboxylic acid：Oxalic acid, butanedioic acid, benzoic acid, citric acid, acetic acid, lactic acid etc.
Phosphate cpd：The various acid such as phosphoric acid, phosphorous acid, its salt etc.
Boron compound：Boric acid class, borate, borate, boron hydride class etc..
In addition, various additives other than the above can be compounded in the resin combination as needed.Add as such
Plus the example of agent, antioxidant, plasticizer, heat stabilizer, ultra-violet absorber, antistatic additive, lubricant, coloring can be included
Agent, filler and other high-molecular compounds, they can be blended in the range of the action effect of the present invention is not damaged.Make
For the concrete example of additive, following such additive can be included.
Antioxidant：2,5 di tert butyl hydroquinone, DBPC 2,6 ditertiary butyl p cresol, 4,4 '-thiobis-（The tertiary fourths of 6-
Base phenol）, 2,2 '-methylene-bis--（4- methyl-6-tert-butylphenols）, octadecyl -3-（3 ', 5 '-di-t-butyl -4 '-hydroxyl
Base phenyl）Propionic ester, 4,4 '-thiobis-（6- tert-butyl phenols）Deng
Plasticizer：Diethyl phthalate, dibutyl phthalate, dioctyl phthalate, wax, liquid stone
Wax, phosphate etc.
Ultra-violet absorber：Ethene -2- -3,3 '-diphenylacrylates of cyano group ester, 2-（2 '-hydroxyl -5 '-aminomethyl phenyl）
BTA, 2-（2 '-hydroxyl -5 '-aminomethyl phenyl）BTA, 2-（2 '-hydroxyl -5 '-aminomethyl phenyl）BTA, 2-
（2 '-hydroxyl -3 '-the tert-butyl group -5 '-aminomethyl phenyl）5- chlorobenzotriazoles, ESCALOL 567,2,2 '-dihydroxy
Base -4- methoxy benzophenones etc.
Antistatic additive：It is pentaerythritol monostearate, sorbitan-monopalmityl ester, sulphation TPO, poly-
Oxirane etc.
Lubricant：Vinyl bis-stearamides, butyl stearate.
As long as in addition, not damaging the scope of the object of the invention, then it can be compounded EVOH in the resin combination（A）、
Supple resin（B）Outside thermoplastic resin, heat-curing resin.As thermoplastic resin, polyolefin, polyamides can be included
Amine, polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene etc..As heat-curing resin, epoxy resin, third can be included
Olefin(e) acid resin, polyurethane resin, polyester resin, a kind of independent or mixture of the modifier of these resins etc..To above-mentioned resin
EVOH is compounded in composition（A）, supple resin（B）Outside resin when, its compounding amount is preferably below 50 mass %, more preferably
For below 10 mass %.
[preparation of resin combination]
The preparation method of the resin combination is not particularly limited, and can include：By EVOH（A）（Or include EVOH conducts
The resin of principal component, it is same as below）With supple resin（B）Dry-mixed and melting mixing method；Make supple resin（B）With height
Concentration, which is matched somebody with somebody, is mixed in EVOH（A）A part and the masterbatch that is granulated, by itself and remaining EVOH（A）Dry-mixed and melting mixing
Method etc..Among these, by EVOH（A）With supple resin（B）Dry-mixed and melting mixing method can be uniform by each composition
Ground is blended, so it is preferred that.Supple resin（B）For the modified supple resin of acid（b1）With unmodified supple resin（b2）Mixture
When, to EVOH（A）The supple resin of middle compounding（B）It can be the modified supple resin of acid（b1）With unmodified supple resin（b2）'s
Dry-blend or by the modified supple resin of acid（b1）With unmodified supple resin（b2）Advance melting mixing and the grain granulated
Material.It is used as the preparation method of the resin combination, it is therefore particularly preferred that by EVOH（A）, the modified supple resin of acid（b1）And not
Modified supple resin（b2）Dry-mixed and melting mixing method.
As the means of the melting mixing for preparing the resin combination, it is not particularly limited, such as spiral shell can be included
Ribbon blender, super mixer-co-kneader（high-speed mixer-cokneader）, mixing mill, extruder（Single spiral shell
Bar or double screw extruder etc.）, intensive mixer etc..Among these, it is preferable to use the side of single screw rod or double screw extruder
Method.The temperature of melting mixing can pass through the species for the resin to be used, molecular weight, the compounding ratio of composition or forming machine
Species etc. is suitably selected, usually 170 ~ 350 DEG C of scope.
When carrying out melting mixing using extruder, it is preferred that using the high extruder of mixing degree, hopper port is entered with nitrogen
Row sealing, is extruded at low temperature.By so operating, can make dispersity become uniformly, suppress the generation of gel or foreign matter
Or be mixed into.
[blow-molded container]
The blow-molded container of the present invention has above-mentioned resin composition layer in innermost layer, therefore maintains EVOH（A）It is former
This oxygen-barrier property, organic solvent resistance, and not only side bottom surface, corner impact strength it is excellent, pressing section is rushed
Hit intensity is also excellent, and the impact of whereabouts during to actual use etc. has high patience.
As the method for the blow-molded container for making the present invention, the method that Coextrusion Blow Moulding can be used.As
Coextrusion Blow Moulding method, applicable so-called direct blow molding method is squeezed using the multilayer at least with 2 extruders
Go out machine, above-mentioned resin combination, other thermoplastic resins and adhesive resin as needed are supplied to different extrusions
Machine, is kneaded, melting extrusion respectively, by each layer with multilayer parison（parison）The inside of mold for forming is firm from mould
The mode that outside after tool ejection is closely collaborated is extruded, and the multilayer parison of tubulose is obtained, then by the parison with molten condition
Blow molding is carried out, so as to obtain laminated vessel.That is, the blow-molded container with compressed part of the invention is directly to be blow molded into
Type container.During the blow molding of direct blow molding method, parison is clamped with a pair of blow moldings with mould, cutting for parison is carried out
Break and relative cutting portion is occurred welding, so as to form compressed part.Extrusion temperature during blow molding can be according to being used
The species of resin, molecular weight, the species of the compounding ratio of composition or forming machine etc. suitably select, usually 170 ~
350 DEG C of scope.
From the viewpoint of mechanical strength etc. is improved, the layer of blow-molded container of the invention constitute have by including at least
Sandwich construction obtained from more than 2 layers of above-mentioned resin combination layer stackup.It is used as by using above-mentioned resin composition layer
The layer of the contact content of the innermost layer of container, i.e. container, can prevent being swelled for caused by content container.With contacting content
Preferably there is the thermoplastic resin layer outside EVOH compared to the layer closer to outside in the innermost layer of thing.
Specifically, constituted as the layer of the blow-molded container, the layer obtained by above-mentioned resin combination is expressed as
When the layer that E, the layer obtained by adhesive resin be expressed as Ad, is obtained by the thermoplastic resin outside EVOH is expressed as T, it can illustrate
Go out following layer to constitute.Left side represents internal layer.Herein, as Ad, carboxyl acid modified polyolefin, especially Malaysia can compatibly be used
Anhydride modified polyolefin.As T, straight-chain low density polyethylene (LDPE), low density polyethylene (LDPE), medium density polyethylene, height can be included
Density polyethylene, vinyl-vinyl acetate copolymer, ethylene-propylene copolymer, polypropylene, propylene-alpha-olefin copolymers（Carbon
The alpha-olefin of atomicity 4 ~ 20）, polybutene, a kind of independent or its copolymer of the alkene such as polypenthylene；Poly terephthalic acid second two
The polyester such as alcohol ester, polyester elastomer, nylon-6, nylon-6,6 grade polyamides, polystyrene, polyvinyl chloride, poly- inclined dichloro
Ethene, acrylic resin, vinyl esters system resin, polyurethane elastomer, makrolon, polyvinyl chloride, polychloroprene etc., can
Compatibly use high density polyethylene (HDPE), polypropylene.
2 layers of E/Ad
3 layers of E/Ad/T, E/Ad/E
4 layers of E/Ad/E/Ad
5 layers of E/Ad/T/Ad/E, E/Ad/E/Ad/T.
The thickness of each layer in the blow-molded container can not be constituted according to layer, purposes, required physical property etc. are come without exception
In, for example as described below.It should be noted that resin composition layer, adhesive resin layer, other thermoplastic resin layers it
In more than 2 layers of at least one kind of layer of presence when, following numerical value are the aggregate values of the thickness of layer of the same race.
Above-mentioned resin composition layer is more than 10 μm and less than 500 μm, preferably more than 20 μm and less than 300 μm, more excellent
Elect more than 50 μm and less than 200 μm as.When resin composition layer is excessively thin, exists and be difficult to obtain inclining by the effect of the invention brought
To, when resin composition layer is blocked up, exist melt-moldability reduction tendency.Other thermoplastic resin layers be more than 100 μm and
Less than 6000 μm, preferably more than 200 μm and less than 4000 μm, more preferably more than 300 μm and less than 2000 μm.Other thermoplastics
Property resin bed it is excessively thin when, there is the side bottom surface of the blow-molded container, the tendency of the impact strength reduction in corner, Qi Tare
When plastic resin layers are blocked up, there is the tendency of melt-moldability reduction.Adhesive resin layer be usually more than 2 μm and 250 μm with
Under, be preferably more than 5 μm and less than 150 μm, be more preferably more than 10 μm and less than 100 μm.
In addition, for the blow-molded container, the multilayer structure making produced when can also be by comprising blow molding
Corner material（scrap）Recovery layer replace thermoplastic resin layer and/or adhesive resin layer to use.Furthermore it is also possible to mix it
The corner material of its polyolefin formed body is used.
[flask for medicinal preparations]
The blow-molded container of the present invention is preferably used as flask for medicinal preparations.The flask for medicinal preparations is the bottle for accommodating liquid medicament.
The present invention blow-molded container not only side bottom surface, corner impact strength it is excellent, the impact strength of pressing section is also excellent,
The impact of whereabouts during to actual use etc. has high patience, therefore is useful as flask for medicinal preparations, pesticide bottle.Herein, liquid
Shape medicament is represented containing agricultural chemicals such as solution, dispersion liquid, the suspension of aromatic hydrocarbon such as various organic medicaments, toluene, dimethylbenzene.Make
For agricultural chemicals, the agricultural chemicals such as containing organophosphor system, the emulsion agent of pyrethroid based compound can be included.
The flask for medicinal preparations is tested based on pesticide bottle with the falling impacts that ortho-test is UN standards（At -18 DEG C, by
1.2m height falls）In have excellent low-temperature impact resistance effect.The capacity of the medicine container of the present invention is 0.1 ~ 100L,
Specifically, preferably 0.5 ~ 50L capacity, more preferably 1 ~ 25L capacity.
[impact strength]
In the present invention, the physical property for the above-mentioned resin combination that innermost layer is used can significantly influence the side of the blow-molded container
The impact strength of face bottom surface, the impact strength in corner and pressing section.Thus, below in an example, should as expression
The side bottom surface of blow-molded container, the index of the impact strength in corner, injection moulding is passed through using by above-mentioned resin combination
And notched cantilever-type impact strength at 23 DEG C, -20 DEG C of injection piecess made is evaluated.In addition, pressing section is
The part that the parison of blow molding is bonded with molten condition, therefore the mutual adhesive strength of resin when can influence to melt.
Thus, below in an example, when above-mentioned resin combination is carried out into injection moulding, in the centrally disposed weld part of injection piecess
Position, compression intensity is evaluated using the cantilever-type impact strength of the welding position of gained injection piecess.
Embodiment
Hereinafter, the present invention is further illustrated by embodiment, but the present invention is not subject to any limitation.Need explanation
It is that the evaluation of gained resin combination etc. is carried out in accordance with the following methods.
[EVOH（A）Ethylene unit containing ratio and saponification degree]
By with DMSO-d6It is used as solvent1H-NMR is determined（Use " the JNM-GX- of Jeol Ltd.'s manufacture
500 types "）To obtain EVOH（A）Ethylene unit containing ratio and saponification degree.
[melt viscosity（MFR）]
Use fusion index instrument（" L244 " of Takara KK's industry manufacture）, in 210 DEG C of temperature, load 2160g bar
The rate of outflow of sample is determined under part（G/10 minutes）, obtain melt flow rate (MFR)（MFR）.
[Shore hardness]
Using sclerometer, according to ISO 7619, the A type Shore hardness of sample is determined.
[the modified supple resin of acid（b1）Acid number]
By making the modified supple resin of acid（b1）Dimethylbenzene is dissolved in, phenolphthalein is used as indicator, 0.05mol/L hydrogen is added dropwise
Potassium oxide-ethanol solution calculates acid number.
[discrete particles diameter and particle wall spacing]
The immediate vicinity of the injection piecess obtained by using slicer in embodiment and comparative example cuts out section, 120
DEG C dimethylbenzene in dipping the several seconds so that supple resin（B）After dissolution, scanning electron microscope is used（SEM）（Hitachi
High-Technologies Corporation SEM " S-2250N "）Multiplying power with 3000 times is divided
The observation of bulk state.Thereafter, using the SEM photograph of 3000 times captured of multiplying power, image analysis software Image-Pro is used
Plus J（Media Cybernetics, Inc. systems）To calculate discrete particles diameter.In addition, being calculated using following calculating formula
Go out particle wall spacing d.
[mathematical expression 2]
Above-mentioned formula（I）In, r is supple resin（B）The radiuses of discrete particles, V be supple resin（B）Volume fraction.
[cantilever-type impact strength]
Use digital shock machine（Toyo Co., Ltd.'s essence mechanism makees made）, according to JIS K7110, in embodiment and
The injection piecess obtained in comparative example（80×10×4mm）On be carved into breach, determine outstanding under conditions of 23 DEG C/50%RH and -20 DEG C
Arm beam type impact strength.
[weld strength]
Use digital shock machine（Toyo Co., Ltd.'s essence mechanism makees made）, pendulum is installed so that central part has weldering
The injection piecess of wiring（80×10×4mm）Cause destruction from sealing wire, beam type punching is determined under conditions of 23 DEG C, 50%RH
Hit intensity（Weld strength）.
Embodiment 1
EVOH will be used as（A）EVOH（A1）（Kuraray Co., Ltd.“EVAL F171”）80 mass parts, as soft
Barras（B）MAh-EB（b1-1）（Maleic anhydride modified ethylene-butene copolymer）（Mitsui Chemicals, Inc's manufacture
“Tafmer MH7010”）10 mass parts and EB（b2-1）（Ethylene-butene copolymer）（Mitsui Chemicals, Inc's manufacture
“Tafmer A4050”）The progress of 10 mass parts is dry-mixed, using following melting mixing condition, is melted using double screw extruder
Melt mixing, granulation, dried 6 hours with 80 DEG C using air drier, so as to obtain resin combination（1）.Then, using resin
Composition（1）, using following injection moulding condition, using injection (mo(u)lding) machine, make 80 × 10 × 4mm injection piecess.In addition,
By two cast gates of more mold exchange and setting, so as to make 80 × 10 × 4mm injection piecess that there is sealing wire at center.
[melting mixing condition]
Device：26(Toyo Co., Ltd.'s essence mechanism makees manufactured " Labo Plastomill to double screw extruder
15C300”)
L/D：25
Screw rod：At a fully engaged type in the same direction
Nib number：2 holes (3)
Extrusion temperature：Supply unit/compression unit/measurement unit/mould=200 DEG C/230 DEG C/230 DEG C/230 DEG C
Rotating speed：100rpm
Discharge-amount：About 5kg/hr
Dry：80 DEG C, 6 hours of heated-air drying.
[injection moulding condition]
Device：Injection (mo(u)lding) machine（" the FS-80S 12AS " of Nissei Plastic Industrial Co., Ltd's manufacture）
Cylinder temperature：Rear portion/middle part/front portion/nozzle=200 DEG C/220 DEG C/220 DEG C/200 DEG C
Mold temperature：60℃.
Resin combination is evaluated by the above method（1）MFR and gained injection piecess discrete particles diameter, particle
Distance, cantilever-type impact strength and weld strength between wall.Gained injection piecess have EVOH（A）For matrix phase and supple resin
（B）For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 2
Except using EVOH（A2）（Kuraray Co., Ltd.“EVAL L171”）It is used as EVOH（A）Outside, utilize
Method same as Example 1, obtains resin combination（2）.Then, using method same as Example 1, using being injected into
Type machine, has made 80 × 10 × 4mm injection piecess and 80 × 10 × 4mm center has the injection piecess of sealing wire.
Resin combination is evaluated by the above method（2）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 3
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）20 mass parts are used as supple resin（B）Outside, utilize side same as Example 1
Method, obtains resin combination（3）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 have been made
There are the injection piecess of sealing wire in × 4mm injection piecess and 80 × 10 × 4mm center.
Resin combination is evaluated by the above method（3）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 4
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）10 mass parts, EB（b2-2）（" the Tafmer of Mitsui Chemicals, Inc's manufacture
A4085”）10 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（4）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess and 80 have been made
There are the injection piecess of sealing wire in × 10 × 4mm center.
Resin combination is evaluated by the above method（4）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 5
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）5 mass parts, EB（b2-2）（" the Tafmer of Mitsui Chemicals, Inc's manufacture
A4085”）15 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（5）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess and 80 have been made
There are the injection piecess of sealing wire in × 10 × 4mm center.
Resin combination is evaluated by the above method（5）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 6
Except using EVOH（A1）85 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）10 mass parts, EB（b2-2）（" the Tafmer of Mitsui Chemicals, Inc's manufacture
A4085”）5 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（6）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess and 80 have been made
There are the injection piecess of sealing wire in × 10 × 4mm center.
Resin combination obtained by being evaluated as the above method（6）MFR and gained injection piecess dispersion particle diameter, particle
Distance, cantilever-type impact strength and weld strength between wall.Gained injection piecess have EVOH（A）For matrix phase and supple resin
（B）For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 7
Except using EVOH（A1）90 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）10 mass parts are used as supple resin（B）Outside, utilize side same as Example 1
Method, obtains resin combination（7）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 have been made
There are the injection piecess of sealing wire in × 4mm injection piecess and 80 × 10 × 4mm center.
Resin combination is evaluated by the above method（7）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 8
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-EP（b1-3）（Maleic anhydride modified second
Alkene-propylene copolymer）（" the Tafmer MP0610 " of Mitsui Chemicals, Inc's manufacture）10 mass parts, EP（b2-3）（Ethene-
Propylene copolymer）（" the Tafmer P0280 " of Mitsui Chemicals, Inc's manufacture）10 mass parts are used as supple resin（B）It
Outside, using method same as Example 1, resin combination is obtained（8）.Then, using method same as Example 1, make
With injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess are made and 80 × 10 × 4mm center have the injection piecess of sealing wire.
Resin combination is evaluated by the above method（8）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Embodiment 9
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-SEBS（b1-4）（It is maleic anhydride modified
Styrene-ethylene/butylene-styrene block copolymer）（" the Tuftec M1911 " of Asahi Kasei Corporation's manufacture）10 mass
Part, SEBS（b2-4）（Styrene-ethylene/butylene-styrene block copolymer）（" the Tuftec of Asahi Kasei Corporation's manufacture
H1041”）10 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（9）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess and 80 have been made
There are the injection piecess of sealing wire in × 10 × 4mm center.
Resin combination is evaluated by the above method（9）MFR and the dispersion particle diameters of gained injection piecess, particle wall between
Distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）For
The island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 3.
Comparative example 1
Use EVOH（A1）It is used as EVOH（A）, without using supple resin（B）, using method same as Example 1,
Using injection (mo(u)lding) machine, 80 × 10 × 4mm injection piecess are made and 80 × 10 × 4mm center have the injection of sealing wire
Piece.
The cantilever-type impact strength and weld strength of injection piecess obtained by being evaluated as the above method.By used tree
The physical property of fat is shown in table 1, evaluation result is shown in table 4.
Comparative example 2
Except using EVOH（A1）95 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）5 mass parts are used as supple resin（B）Outside, using method same as Example 1,
Obtain resin combination（10）.Then, using method same as Example 1, using injection (mo(u)lding) machine, make 80 × 10 ×
There are the injection piecess of sealing wire in 4mm injection piecess and 80 × 10 × 4mm center.
Resin combination is evaluated by the above method（10）MFR and gained injection piecess dispersion particle diameter, particle wall
Between distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）
For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Comparative example 3
Except using EVOH（A1）90 mass parts are used as EVOH（A）, use EB（b2-2）（Mitsui Chemicals, Inc's system
" the Tafmer A4085 " made）10 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain
Resin combination（11）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm has been made
Injection piecess and 80 × 10 × 4mm center there are the injection piecess of sealing wire.
Resin combination is evaluated by the above method（11）MFR and gained injection piecess dispersion particle diameter, particle wall
Between distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）
For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Comparative example 4
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use EB（b2-2）（Mitsui Chemicals, Inc's system
" the Tafmer A4085 " made）20 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain
Resin combination（12）.Then, using method same as Example 1, using injection (mo(u)lding) machine, 80 × 10 × 4mm has been made
Injection piecess and 80 × 10 × 4mm center there are the injection piecess of sealing wire.
Resin combination is evaluated by the above method（12）MFR and gained injection piecess dispersion particle diameter, particle wall
Between distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）
For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Comparative example 5
Except using EVOH（A1）80 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）1 mass parts, EB（b2-2）（" the Tafmer of Mitsui Chemicals, Inc's manufacture
A4085”）19 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（13）.Then, using method same as Example 1, using injection (mo(u)lding) machine, made 80 × 10 × 4mm injection piecess and
There are the injection piecess of sealing wire in 80 × 10 × 4mm center.
Resin combination is evaluated by the above method（13）MFR and gained injection piecess dispersion particle diameter, particle wall
Between distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）
For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Comparative example 6
Except using EVOH（A1）70 mass parts are used as EVOH（A）, use MAh-EB（b1-2）（Mitsui Chemicals, Inc
" the Tafmer MA8510 " of society's manufacture）10 mass parts, EB（b2-2）（" the Tafmer of Mitsui Chemicals, Inc's manufacture
A4085”）20 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（14）.Then, using method same as Example 1, using injection (mo(u)lding) machine, made 80 × 10 × 4mm injection piecess and
There are the injection piecess of sealing wire in 80 × 10 × 4mm center.
Resin combination is evaluated by the above method（14）MFR and gained injection piecess dispersion particle diameter, particle wall
Between distance, cantilever-type impact strength and weld strength.Gained injection piecess have EVOH（A）For matrix phase and supple resin（B）
For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Comparative example 7
Except using EVOH（A1）90 mass parts are used as EVOH（A）, use Japanese Patent Laid-Open 2010-95315 public affairs
The polymer with polyalkylene ether unit described in report is MAh-TPEE（b1-5）（Maleic anhydride modified thermoplastic polyester bullet
Property body）10 mass parts are used as supple resin（B）Outside, using method same as Example 1, obtain resin combination
（15）.Then, using method same as Example 1, using injection (mo(u)lding) machine, made 80 × 10 × 4mm injection piecess and
There are the injection piecess of sealing wire in 80 × 10 × 4mm center.
Resin combination obtained by being evaluated as the above method（15）MFR and gained injection piecess dispersion particle diameter,
Distance, cantilever-type impact strength and weld strength between grain wall.Gained injection piecess have EVOH（A）For matrix phase and supple resin
（B）For the island structure of dispersed phase.The physical property of used resin is shown in Tables 1 and 2, evaluation result is shown in table 4.
Embodiment more than：The resin combination shows that excellent izod is strong at room temperature in low temperature
Degree, and the excellent weld strength of display.By using these resin composition layers in innermost layer, using the teaching of the invention it is possible to provide side bottom surface, angle
The impact strength in portion and the excellent blow-molded container of the impact strength of pressing section.
On the other hand, the EVOH of comparative example 1（A）The cantilever-type impact strength of itself is weak, has used EVOH（A）Itself
The side bottom surface of blow-molded container, the impact strength in corner are insufficient.
As comparative example 2, even containing EVOH（A）And supple resin（B）Resin combination, but EVOH（A）With
Supple resin（B）Mass ratio [（A）/（B）] outside 75/25 ~ 90/10 scope, EVOH（A）Ratio it is many when, beam type
Impact strength is weak, has used the impact strength in the side bottom surface of the blow-molded container of the resin combination, corner insufficient.
As comparative example 3,4 and 5, even containing EVOH（A）And supple resin（B）Resin combination, and EVOH
（A）With supple resin（B）Mass ratio [（A）/（B）] in the range of 75/25 ~ 90/10, but the particle wall spacing of dispersed phase
During more than 0.3 μm, cantilever-type impact strength and weld strength are weak, have used the blow-molded container of these resin combinations
The impact strength of side bottom surface, the impact strength in corner and pressing section is insufficient.
As comparative example 6, even containing EVOH（A）And supple resin（B）Resin combination, and of dispersed phase
Distance is less than 0.3 μm between grain wall, but EVOH（A）With supple resin（B）Mass ratio [（A）/（B）] 75/25 ~ 90/10
Scope is outer and supple resin（B）Ratio it is big when, although the cantilever-type impact strength of low temperature at room temperature is excellent, weld strength
It is weak, use the impact strength of the pressing section of the blow-molded container of these resin combinations insufficient.
On the other hand, as comparative example 7, even containing EVOH（A）And supple resin（B）Resin combination, and
EVOH（A）With supple resin（B）Mass ratio [（A）/（B）] in the range of 75/25 ~ 90/10, the particle wall spacing of dispersed phase
From for less than 0.3 μm, but supple resin（B）During for beyond styrene series thermoplastic elastomer or alpha olefin copolymer, although outstanding
Arm beam type impact strength is abundant, but weld strength is weak, has used the pressing section of the blow-molded container of these resin combinations
Impact strength it is insufficient.
Embodiment 10
The resin combination of embodiment 1 is used as resin combination（1）, be used as polypropylene（PP）And use Japan poly-
Propylene Co., Ltd. manufacture " Novatec PP EA7A ", is used as adhesive resin（Tie）And use Mitsui Chemicals, Inc
Manufacture " ADMER QF500 " have made layer composition（Left side represents internal layer）：Resin combination（1）/Tie/PP=115μm/40μ
M/690 μm, capacity：1000mL, surface area：680cm2The blow-molded container with compressed part.Hold to gained blow molding
Ethylene glycol is injected in device in the way of reach capacity 98%, -18 DEG C are cooled to.On the blow-molded container after cooling, carry out
Make its horizontal drop test fallen from 1.2m height in the way of turning into shock point sideways and it is turned into corner
The diagonal drop test that the mode of shock point falls.As a result, in any experiment, container is not cracked, not
Generation leakage.
Comparative example 8
Use EVOH（A1）, be used as polypropylene（PP）And " the Novatec PP for using Japan Polypropylene Corp. to manufacture
EA7A ", it is used as adhesive resin（Tie）And use Mitsui Chemicals, Inc manufacture " ADMER QF500 " have made layer structure
Into（Left side represents internal layer）：EVOH（A1）/ Tie/PP=115 μm/40 μm/690 μm, capacity：1000mL, surface area：680cm2's
Blow-molded container with compressed part.Ethylene glycol is injected in the way of reach capacity 98% into gained blow-molded container,
It is cooled to -18 DEG C.On the blow-molded container after cooling, operate to carry out horizontal drop test and right similarly to Example 10
Linea angulata drop test.As a result, being cracked sideways in horizontal drop test, occurring leakage, in diagonal drop test
Middle corner cracks, occurs leakage.
Comparative example 9
The resin combination of comparative example 6 is used as resin combination（14）, be used as polypropylene（PP）And use Japan
Polypropylene Co., Ltd. manufacture " Novatec PP EA7A ", is used as adhesive resin（Tie）And use Mitsui Chemicals, Inc
Society manufacture " ADMER QF500 " have made layer composition（Left side represents internal layer）：Resin combination（14）/Tie/PP=115μm/
40 μm/690 μm, capacity：1000mL, surface area：680cm2The blow-molded container with compressed part.To gained blow molding
Ethylene glycol is injected in container in the way of reach capacity 98%, -18 DEG C are cooled to.On the blow-molded container after cooling, with
Embodiment 10 equally operates to carry out horizontal drop test and diagonal drop test.As a result, in any experiment, compressing
Portion cracks, occurs leakage.
Claims (6)
1. Coextrusion Blow Moulding laminated vessel, it is characterised in that it holds for the Coextrusion Blow Moulding multilayer with compressed part
Device, has in innermost layer and contains ethylene-vinyl alcohol copolymer（A）And supple resin（B）Resin composition layer；
Supple resin（B）For styrene series thermoplastic elastomer or alpha olefin copolymer,
Ethylene-vinyl alcohol copolymer（A）With supple resin（B）Mass ratio [（A）/（B）] in the range of 75/25 ~ 90/10,
With ethylene-vinyl alcohol copolymer（A）For matrix phase, supple resin（B）For the island structure of dispersed phase, and
The particle wall spacing of the dispersed phase is less than 0.3 μm.
2. the Coextrusion Blow Moulding laminated vessel described in claim 1, wherein, the institute measured under 210 DEG C, 2160g loads
State the melt flow rate (MFR) of resin combination（MFR）For ethylene-vinyl alcohol copolymer（A）Melt flow rate (MFR)（MFR）2/3
Below.
3. the Coextrusion Blow Moulding laminated vessel described in claim 1 or 2, wherein, supple resin（B）For the modified soft tree of acid
Fat（b1）With unmodified supple resin（b2）Mixture.
4. the Coextrusion Blow Moulding laminated vessel described in claim 1 or 2, the supple resin measured according to ISO 7619（B）
A types Shore hardness be less than 90.
5. the Coextrusion Blow Moulding laminated vessel described in claim 1 or 2, it is flask for medicinal preparations.
6. the Coextrusion Blow Moulding laminated vessel described in claim 5, the medicament is agricultural chemicals.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012110160 | 2012-05-14 | ||
| JP2012-110160 | 2012-05-14 | ||
| PCT/JP2013/062901 WO2013172226A1 (en) | 2012-05-14 | 2013-05-08 | Blow-molded container with pinch-off part |
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| Publication Number | Publication Date |
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| CN104271453A CN104271453A (en) | 2015-01-07 |
| CN104271453B true CN104271453B (en) | 2017-08-08 |
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| CN201380024813.8A Active CN104271453B (en) | 2012-05-14 | 2013-05-08 | Blow-molded container with compressed part |
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| Country | Link |
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| US (1) | US10293968B2 (en) |
| EP (1) | EP2851308B1 (en) |
| JP (1) | JP6168561B2 (en) |
| CN (1) | CN104271453B (en) |
| BR (1) | BR112014027699B1 (en) |
| ES (1) | ES2633933T3 (en) |
| WO (1) | WO2013172226A1 (en) |
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| JP6653967B2 (en) * | 2016-05-27 | 2020-02-26 | 株式会社吉野工業所 | Humidity control container |
| WO2018084187A1 (en) | 2016-11-02 | 2018-05-11 | 株式会社クラレ | Multilayer structure and use of same |
| JP6927922B2 (en) * | 2017-05-24 | 2021-09-01 | 株式会社クラレ | Crosslinkable resin compositions and crosslinked products, their production methods, and multilayer structures. |
| EP3476594A1 (en) | 2017-10-24 | 2019-05-01 | Renolit SE | Laminate structure for biocompatible barrier packaging |
| EP3476593A1 (en) * | 2017-10-24 | 2019-05-01 | Renolit SE | Laminate structure for barrier packaging |
| JP7126387B2 (en) * | 2018-06-27 | 2022-08-26 | 株式会社クラレ | LAYER STRUCTURE, MOLDED BODY AND METHOD FOR MANUFACTURING THE SAME |
| US11400694B2 (en) | 2018-08-30 | 2022-08-02 | Kuraray Co., Ltd. | Multilayer article suitable for use of storage bag for agricultural products |
| JP7184932B2 (en) | 2019-01-30 | 2022-12-06 | 株式会社クラレ | Multilayer structure, packaging material comprising the same, and vertical form-fill-seal bag |
| JP7339742B2 (en) * | 2019-02-26 | 2023-09-06 | 株式会社クラレ | multilayer film |
| JP7339020B2 (en) * | 2019-05-22 | 2023-09-05 | 株式会社クラレ | Resin composition containing ethylene-vinyl alcohol copolymer, molded article and multilayer structure |
| EP4282915A1 (en) * | 2021-01-25 | 2023-11-29 | Mitsubishi Chemical Corporation | Ethylene-vinyl alcohol copolymer composition |
| DE102021121806A1 (en) * | 2021-08-23 | 2023-02-23 | Gaplast Gmbh | Container consisting of a rigid outer container and a deformable inner bag and method for manufacturing such a container |
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| CN1536019A (en) * | 2002-12-12 | 2004-10-13 | �����ɷ� | Thermoplastic polymer composition, forming article and multilayer sturcture |
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| JP3481649B2 (en) * | 1993-06-14 | 2003-12-22 | 株式会社クラレ | Resin molding |
| JP2776300B2 (en) * | 1995-05-31 | 1998-07-16 | 日本電気株式会社 | Audio signal processing circuit |
| JPH09241475A (en) * | 1996-03-05 | 1997-09-16 | Toray Ind Inc | Chemical-resistant thermoplastic resin composition and molded product therefrom |
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| JP4727037B2 (en) * | 2000-01-28 | 2011-07-20 | 株式会社クラレ | Co-injection stretch blow molded container |
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| JP5361632B2 (en) * | 2008-09-22 | 2013-12-04 | 日本合成化学工業株式会社 | Agricultural container |
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| JP5392658B2 (en) * | 2010-03-31 | 2014-01-22 | 株式会社吉野工業所 | Laminated blow housing |
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2013
- 2013-05-08 BR BR112014027699-4A patent/BR112014027699B1/en active IP Right Grant
- 2013-05-08 JP JP2014515577A patent/JP6168561B2/en active Active
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- 2013-05-08 WO PCT/JP2013/062901 patent/WO2013172226A1/en active Application Filing
- 2013-05-08 CN CN201380024813.8A patent/CN104271453B/en active Active
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| CN1536019A (en) * | 2002-12-12 | 2004-10-13 | �����ɷ� | Thermoplastic polymer composition, forming article and multilayer sturcture |
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| JPWO2013172226A1 (en) | 2016-01-12 |
| WO2013172226A1 (en) | 2013-11-21 |
| JP6168561B2 (en) | 2017-07-26 |
| ES2633933T3 (en) | 2017-09-26 |
| US20150144523A1 (en) | 2015-05-28 |
| CN104271453A (en) | 2015-01-07 |
| EP2851308B1 (en) | 2017-07-12 |
| EP2851308A1 (en) | 2015-03-25 |
| BR112014027699B1 (en) | 2021-03-30 |
| BR112014027699A2 (en) | 2017-06-27 |
| EP2851308A4 (en) | 2015-12-02 |
| US10293968B2 (en) | 2019-05-21 |
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